Carbamylguanamines



Patented Nov. 2, 1943 2 333 452 iassalsz "CARBAMYLGUANAMINES:

. -.:Jack-Theo" Thurston; Cos Cob; and? Daniel Elmer I -Nagy,:Stamford, Conn., assignors to-American 1 Cyanamid Company, New York, N.'Y.,l a corporation of Maine zumreo PATENT or ice- No Drawing. Application Augu'steiio, 1941,

Serial No. 409,132

13 Claims. (cuzso zisl This invention relateslto guanaminesin which their surfaceeactiveamide group areparticularly the 2-carbonatom of the4,6-diamino-1,3,5-triuseful -.asit'extile 'finishing-qand water-repellent azine ring contains a the substituentgroupta agents. I carboxylic acid amide-which maybe either ali- The invention will be described in greateradephatic or aromatic,-and referred to intthe-specifi- 5 tail intconjunction with the fOlIOWlIlgSPECifiC'tBX- cation and. claimsascarbamylguanamines. amples. Thesparts are by weight.

According' to the present invention carbamyl- E guanamines of .the :aliphaticand. aromatic series can be: prepared "by various methodsincluding 1o-N-0ctylmrbamylbenzoguammme thereaction'of'anester-ramide'of: azdibasic'acid vl0 with" biguanideat'roomtemperatur or with w 1 CONHGBHll gentle heating. .Therester group reactswith the .biguanidej to form.the:diaminotriazine ring and the amide group remainslattached to theresidue of the acid which is connected to thei2'ecarb0n lam-c g-NH: atom of r they triazine: ringi 11: The: products; of the present invention can be prepared in water'solution although not-as high. yields are obtained as when organic solventssuchasithe lower. mono- .hydric paraffirji alcohols. are used ,..as solvents. Wh le the present invention is not limitedto. any particular process ofinakin'gthe. compounds; .the reaction of the ester amides with a biguanide .in a-sllltable'rsolventis l i s at g reaction mixture was practicallysolid. After galmc i gp ag izm ed w lw W l-.- standing overnight, the product'was removed by 2525a; altittf siih a ifitfifi $232, 93; fimtim i t thirfilimtegofirnmd 13 i l more pro uc. e yie of crude -oc yethyl ether of ethylenewglycolr and the carbamylbenzoguanaminev melting at 168 C. was

These alcohols.are cheap,exce1lent solvents for 61% and after recrystallization from 50% biguanwdes, and operate very satisfactorily in the am] the melting point was raised to process. A further advantage lies in the fact Y M To 25 parts of biguanide dissolvedin 100 parts of methanol was added 83.7 parts of methyl N- octylpht-halamateand '6' parts of? sodium metal dissolved in about. 100 parts or methanol. The product began to crystallize from the-solution in that if an alcohol is chosen corresponding to the EXAMPLE 2 alcohol radical of theester, amide. noseparation 3-N phenylcarbamylpropionoguanamine betweendifierent,alcoholsis required. g f

I 'Among' the most important products from the ,l N practicalstandpointi ai'egthe- Ns-un'substitute'd CONHQ glianamineswhit'shard prepar'edlbylreacting.bi 1 1 guanide itself with ester amides". However; N- HiN' C C-NH:

substituted guanamines can be prepared by using 'j suitable correspondingly substituted biguanides I v j f f such as, for example, phenyl biguanide, allyl bi- "l T0112, parts of 'biguanide dissolved. in 60; parts guanide or dimethyl biguanide. of 'methanolwas added 17.5;parts of succinariil.

The preferred process of the present invention Precipitation which occurred-rapidly gave: the using an ester amide and biguanide reacts readily guanamine melting at 202 203 C. in about 93% without a condensing'agent -whicl'ris an adv'an yield. The product w'ass'oluble in dilute acid, tage, but the invention is not limited to proc'esses hot ethanol; but insolublein-watendilute alkali in which no c'ondensingaagents arezused :and in and cold ethanol.

fact with some of the substituted:biguanidesthe When thereaction was carried out in water reaction is rather slow and a condensing: agent s lution instead of in methanol solution, the yield such as a metal alkoxidevisdesirable to reduce rewas 12%. H

action time and increase yields. When phenyl biguanide was substituted for The products of the present invention may be biguanide itself, the corresponding l-N-phenyl formed into resins with formaldehyde, some of guanami-newasiobtained. The reaction was not which are oil-solublezaand others, by reason of quitezas rapid and theyield was somewhatlower;

about one hour andatytheend of three hours the To 25 parts of biguanide dissolved in 100 parts of methanol was added 72 parts of methyl-N- ate was dissolved in 250 parts of methanol conoctylmaleamate. The reaction mixturebecame deep purple and some productseparated after standing several days. The reaction mixture was di1uted with water which precipitated a dark oily material that was separated from the water; The oily product was extracted with about 1000 parts of hot 2% hydrochloric acid. The free base having the above probabl formula was preparedby neutralization with sodium hydroxide and after recrystallization from a 40% alcohol-water mixture, the product melted at about 92 C.,-and on further drying, the melting point was raised to 146-148 C. The residue from the hydrochloric acid extraction was "extractedwith 1000 parts of hot water, which removed a slightly soluble hydrochloride salt. The free'base was prepared by neutralization with sodium hydroxlde and after recrystallization from a 35% alcohol-water mixture, the product melted at 60-62" C. Further drying raised the melting point to 80 C. This com'pound,,which gave the same analytical data as the above methoxy-N- octylcarbamylpropionoguanamine, and which appears to have the following formula:

C---GHOHzOONHCsHi1 N N 00113 HzNr- C--NH:

undergoes a change on heating above its melting point since it solidifies at about '105-110 C. and melts at 145 C.

EXAMPLE 4 o-c'arbamylbenzoguanamine CONE! Twenty-five parts of biguanide dissolved in 100 parts of methanol was added to 35.5 parts of phthalimide and 5.5 parts of sodium metal dispersed in 120 parts of methanol and the reaction mixture was warmed slightly in order to obtain complete solution. The precipitated product was removed by filtration and washed with a small amount of methanol and water. The yield of o-carbamylbenzoguanamine melting -,at .264+266 'C. after recrystallization from, hot water was slightly less than 60 Y EXAMPLE 5 fl-N-dibutylcarbamylpropio'noguanumine o-oHT-c112ooN-(olm)3 7 To 37 parts of succinic anhydride dissolved 'in 400 parts of toluene wasiadded 52 parts of dibutyltaining 49 parts of biguanide and in a short time product began to precipitate. The insoluble material was'removed by filtration and washed with methanol. Thisproduct, amounting to 22 parts, was identified as succinoguanamine having the following formula:

The original methanol filtrate from the succinoguanamine was evaporated to dryness and the residue was extracted with 1500 parts of hot 1% hydrochloric acid. The B N-dibutyIcarbamyIprO- pionoguanamine was recovered from V the cooled filtrate by neutralization; After recrystallization from 50% ethanol,26 parts of the'product melting at 150-152" C. was"obtained. The low yield was due to the large" amount of dibutyl succinate present in the ester amide.

We claim:

'1. Carbamylguanamines having the following formula: I 5i Am--OC-'RG in which Am. is a member ofth group consisting of. radicals pf, primary amines, secondary amines,and ammonia; R is a radical including in the groupconsisting. of arylenes' and alylenes and'G is a guanaminehaving a free valence on the 2ecarbon atom of the triazine ring; the bond between R. andqbeing'a carbon to-carbon bond.

2 ,Carbamylguanamines having the following formula:

' im-0 CR'-O,

N I HaN- c in which Am .is a member ofthe group consisting of radicals. of primary amines, secondary amines and ammonia, R is a radical included in the groupconsisting of arylenes and alkylenes. 3; carbamylguanamines having ,the following formula:

II I C-NH:

in which Am is a member of the group consisting of radicals of primary amines; secondary amines and ammonia, and Ar is an aryl radical.

- '4. Carbamylguanamines having the following which comprises reacting biguanide with ammonia and. Al is an aliphatic radical.

'5. o-N-0ctylcarbamylbenzoguanamine; 6. 3-N-phenylcarbamylpropionoguanamine. 7.- p N octylcarbamylmethoxypropionoguan amine.

8. A method of preparing a carbamylguanamine which comprises reacting a bi-guanide with an ester amide of a dicarboxylic acid.

9. A method of preparing a carbomylguanamine an ester amide of a. dicarboxylic a'cich 10. A method of preparing o -N-octylcarbamyl- H nide withan ester of N-octylphthalamic acid.-

11. A method of preparing p-N-octylcarbamylmethoxypropionoguanamine whichcomprises reacting biguanlide with an ester ofiNr-octyl malea mic acid in methanol solution.

12. A method according to claim 8 in which the reaction takes place in a solution of a lowermono- I hydric paraflin alcohol. I I

13 A method according to cIaimQ -in which" v the reaction takes-place in a solution of a lower monohydric paraflin alcohol. 7 I

JACK THEO THURVSVTOAN.

Q -DANIEL'EIMERNAGY.

benzoguanamine which comprises reactingbigua- 

